Wool dyestuffs and process of making same



wherein X means hydrogen or a sulfonic acid atented Aug. 161, 1932 UNITED STATES sEoEG KALISGHER, or EEAEKEQET-OE-THE- AIE, Am: Ennsr HONOLD, oE FRANK- Eo T-oN-THE-M m-EEGHENHEIM, GERMANY, ASSIGNORS' TO GENERAL WORKS,ING.,,QF'NEWVYORK,1\T.Y.,A coEroE TIoN 0F nnra wrnus WOOL nYEsTUEEs AND r EocEssoE MAKINGVQVVSAMVE No'Drawingi Application filed. April 24, 1930; Serial b; 447,093, and in eer a ma 18, 1929.

This invention relates to new wool dyestulfiswhich correspond to the generalformu a: 1

V NH,

O NH-R group and R a sulfonated aromatic radical of the group consisting of and These dyestuffs are obtained according to this invention by condensing 1-amino-4-halogeno-anthraquinone-2-sulionic with an aromatic diamino-mono-sulfonic acid of the formula l i V (H) NH:

SOaH

wherein Y means a CC-bond or an iminogroup. 7 q 7 The smooth course of this reaction contrasts with the fact that mono-amino-arylsulfonic acids when condensed with l -amino- 4 halogeno anthraquinone-Qsulfonic acid in an analogous manner, do not yield the corresponding 1-aminoA-sulfoarylamino-anthraquinone-Q-sulfonic acids. r

In order to produce "dyestuffs containing no sulfonic group attached to the anthraquinone nucleus (X in the above formula being hydrogen) the condensation'products may be treated with feebly acting alkaline reducing agents. V

All these products are valuablewool-dyestufl'sdyeing from an acid bath blue to grey to green shades of an excellent fastness.

Even the last mentioneddyestufi's containing only one-sulfonic group show a sufiicient solubility. general properties as the first group of these dyestuffs.v

1 'In orderto further illustrate" our invention the following examples are given, the parts being by weight and all temperatures in Centigrade degrees; but we wish it to be understood that our invention not limited to the particular products nor to the reacting conditions mentioned therein.

Example 1 v I several hours while stirring. From the in-' tensefgreenish blue solution the condensation product is'precipitated'by the addition of common salt. 'Theresidue is treated with 3000- parts of water. The pure dyestuif is Otherwise they show the same ANILIN E 7 precipitated therefrom by "the addition of 20 parts of concentratedhydrochloric acid and washed with water. It corresponds probably to the formulaz' e acid: bath greenish blueshades; :5. .7 i I It dissolves easily in water with the addition of feeble alkalies as soda. Its solution in concentrated sulfuric acid shows a brownish tint which becomes blue by the addition of paraformaldehyde. It dyes wool from an aceticacid bath clear greenish blue shades of a good fastness to light and an excellentfastness to washing and perspiration.

Ewample 50 parts of the sodium "salt of I-amino4- bromo-anthraquinone-Q-sulfonic acid are cone densed with 50 parts of "the sodium salt of d diamino-diphenylan1ine-2-sulfonic acid as described inExample 1. The dyestuif thus produced and purified by precipitating with hydrochloric 'acidicorresponds.probably tothe formular-f NH-ONH-ONH: 7 It dissolves easily in water, even without any addition ofj alkali and dyes wool from an acid bath greyishhlue shades of an excellent fastness. Its solution in concentrated sulfuric acid shows alight bluetint becoming green bythe addition of paraformaldehyde.

Esample 3 parts of the sodium salt of l-a minolbromo-anthraquinone 2ssulfonic acid are condensedwith 50 parts of the sodium salt of 1-cyclohexylamino l-a-minobenzene-2 sulfon ic acid in the manner described-in Example 1. The new dyestuif is purified by'precipitating itstsolution with commonsalt. It corresponds probablyto the formula: W

V NH: 7

SOJH I l O 'NHONH7 FE? V S0311 H2 H2.-

of crystallized sodium sulfide in 300. parts The mixture is boiled for 23 of water. hours under a reflux condenser. Then the solution is filtered and precipitated with common salt. 'llheresidu'eiis washed again s. dissolved in water and precipitated by 10 parts of concentrated hydrochloric acid. The new dyestuff thus produced is nearly insoluble in cold water and is easily obtained in a pure state. It corresponds probably to the formula:

O NHz NHa SOaH

It dissolves easily in water .with an. addition of alkali carbonate or acetate or borax and dyes W0 01 from an acid bath greenish blue shades of an excellent fastness to washing and milling.

The same dyestufi isobtained by treating the dyestuff of Example l-with another al- I kaline reducing agent, as for example with glucose and alkali. 1

We claim:- f

l. A process which comprises condensing '1- amino -lbromo-anthraquinone-Q-sulfonic acid with an aromatic diamino-mono-sulfonic acld of the general formula:

wherein. R means a sulfonated aromatic radical of the group consisting of -OQ -NHnONH l NHZ S|O3H SOaH and n2 H, @NH Hz sloaH H H2 in an aqueous solution in the presence of an acid-binding agent and of a copper-containing catalyst,'and acting on the condensation product .thus formed with analkaline reducing agent.

2. A process which comprises condensing l-amino 4L bromo-anth'r-aquinone 2 sulfonic acid with an aromatic diamino-mono-sulfonic acid of the general formula:

wherein R means a sulfonated'aromatio radical of the group consisti1 1g of in an aqueous solution in the presence of'an acid-binding agent and of acopper conta'ining.catalyst. ;.v I

3. A process which comprises condensing l-amino 4 -bromo-anthraqu1none -2 -sulfonic acid with an aromatic d1am1no-mono-sulfon1 acid of the general formula: r

stuffs corresponding to the probable general wherein Y means a C-C-bond or an imino group, in an aqueous solution in the presence of an acid-binding agent and of a coppercontaining catalyst.

4:. A process which comprises condensing 1 amino 4 bromo-anthraquinone -2'-sulfonic acid with benzidine-mono-sulfonic acid of the formula in an aqueous solution in the presence of an acid-binding agent and of a copper-containing catalyst.

5. As new compounds the acid wool dyestuffs corresponding to the probable general formula Y NM wherein X means hydrogen or a sulfonic acid group and R a sulfonated aromatic radical of the group consisting of S 03H and stuffs corresponding to the probable general formula 1 NH-R wherein R means a sulfonated aromatic radical of the group consisting of:

H: H: a -QB, V A Om H H:

all

which compounds are intense colored powders dyeing wool from an acid bath blue to grey to green shades of an excellent fastness.

7. As new compounds the acid wool dyeformula:

SO|H

wherein Y means a GG-bond or an iminogroup, which compounds are intense colored powders dyeing wool from an acid bath greenish to greyish blue shades of an excellent fastness.

V 8. As a new compound the acid wool dyestuif corresponding to the probable formula:

p NH:

SOaH

tures. r

GEORG KALISCHER.

ERNST HONOLD. 

